CN109081375A - The technique that the Ammonia recovery ammonium and waste water of a kind of vanadium processed are recycled - Google Patents

The technique that the Ammonia recovery ammonium and waste water of a kind of vanadium processed are recycled Download PDF

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CN109081375A
CN109081375A CN201811068047.6A CN201811068047A CN109081375A CN 109081375 A CN109081375 A CN 109081375A CN 201811068047 A CN201811068047 A CN 201811068047A CN 109081375 A CN109081375 A CN 109081375A
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ammonium
vanadium
ammonia
dope
vanadate
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许小弟
李益和
万伟勋
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China Vanadium United Technology Development Co ltd
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Hunan Vanadium Industry Technology Development Co Ltd
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Priority to CN202210746038.8A priority Critical patent/CN114988473A/en
Priority to CN201811068047.6A priority patent/CN109081375A/en
Publication of CN109081375A publication Critical patent/CN109081375A/en
Priority to US16/565,828 priority patent/US10974968B2/en
Priority to RU2019128406A priority patent/RU2710613C1/en
Priority to DE102019124431.5A priority patent/DE102019124431A1/en
Priority to PCT/CN2019/105945 priority patent/WO2020052686A1/en
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G31/00—Compounds of vanadium
    • C01G31/02—Oxides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
    • C01C1/00—Ammonia; Compounds thereof
    • C01C1/02—Preparation, purification or separation of ammonia
    • C01C1/026—Preparation of ammonia from inorganic compounds
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
    • C01C1/00—Ammonia; Compounds thereof
    • C01C1/28—Methods of preparing ammonium salts in general
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G31/00—Compounds of vanadium
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
    • C02F1/54—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using organic material
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
    • C22B3/06—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic acid solutions, e.g. with acids generated in situ; in inorganic salt solutions other than ammonium salt solutions
    • C22B3/08—Sulfuric acid, other sulfurated acids or salts thereof
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
    • C22B3/12—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic alkaline solutions
    • C22B3/14—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic alkaline solutions containing ammonia or ammonium salts
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B34/00—Obtaining refractory metals
    • C22B34/20—Obtaining niobium, tantalum or vanadium
    • C22B34/22—Obtaining vanadium

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Abstract

The invention discloses the technique that a kind of Ammonia recovery ammonium of vanadium processed and waste water are recycled, traditional process for extracting vanadium program is complicated, and is most difficult to control and what is handled is exactly ammonia emission and wastewater treatment.This technique can directly extract ammonium metavanadate and ammonium poly-vanadate since smelting of digging up mine；During high purity vanadic anhydride is made with ammonium metavanadate or ammonium poly-vanadate, can boundling discharge whole ammonias be made ammonium use, it is ensured that exhaust gas zero provide；Using polyacid ester flocculation technique, the whole waste water for generating the above process are effectively addressed, it is ensured that wastewater zero discharge is recycled, and the purity of all products reaches 99.5-99.99%.

Description

The technique that the Ammonia recovery ammonium and waste water of a kind of vanadium processed are recycled
Technical field
The invention belongs to vanadium technology processed fields, and in particular to Ammonia recovery ammonium and the waste water circulation of a kind of vanadium processed make Technique.
Background technique
Vanadium in fields such as steel, non-ferrous metal, chemical industry, alloy, superconductor, auto industrys, is a kind of extensively Important strategic materials.
Vanadium distribution in nature extremely disperses, and exists usually in the form of V (III) and V (IV), wherein V (III) is accounted for Majority, trivalent vanadium can be entered in silicate mineral lattice with class matter in-phase version, meanwhile, tetravalence vanadium can also be with class matter in-phase version It is present in oxygen-octahedron structure.Such ore is difficult to leach, and trivalent or tetravalence vanadium is leached, it is necessary to destroy crystal knot Structure, makes that there are the vanadium in crystal structure to release.
Conventional process for extracting vanadium technology can be summarized as two kinds of representative types: roasting process for extracting vanadium (pyrogenic process vanadium extraction work Skill) and wet process process for extracting vanadium.
Wet process process for extracting vanadium is directly to carry out acidleach to raw ore containing vanadium, is included under higher concentration acid condition, even In the environment of heating pressurization, oxidant exist, the technical process that solution containing vanadium body is obtained in vanadium mineral is realized.Pyrogenic process process for extracting vanadium It is ore by high temperature oxidation roasting, Low Valent Vanadium oxidation is converted into pentavalent vanadium, then carries out wet-leaching and obtain solution containing vanadium body, realizes The technical process of ore vanadium extraction.In roasting process for extracting vanadium, bone coal adds salt sodium oxide baking to form vanadium bearing slag, uses process water Directly leaching (i.e. water logging) obtains the lower leaching liquid of concentration containing vanadium, ammonium chloride precipitation is then added, ammonium metavanadate precipitate is made, It is obtained after roasting vanadic anhydride crude product (thick vanadium), then thick vanadium is obtained into ammonium metavanadate through alkali soluble, removal of impurities, the secondary precipitation of ammonium chloride, The vanadic anhydride product that purity is greater than 98% is obtained after thermal decomposition.To formed " sodium method roasting, two-step method precipitation technique " or " salt is added to roast process for extracting vanadium ", or carried out after lime, lime stone or other calcium containing compounds are made additive and bone coal pelletizing Roasting makes vanadium be oxidized to the calcium salt of vanadium not soluble in water, and recarbonation is leached to be soaked at containing vanadium solution, then with acid or dilute alkaline soln Out.It is subsequent or using hydrolysis precipitation, or use dissolution extraction, or use ion exchange, then using pyrolytic process purification vanadium.
In short, by navajoite stone after adding salt to roast and to form vanadium bearing slag, it is necessary to be leached with water or acid or alkali, make three Valence vanadium, tetravalence vanadium or pentavalent vanadium are leached from vanadium bearing slag to be come out, then using extraction and stripping process, or is made with ion-exchange Vanadic salts is separated with the other compositions in leaching liquid, and final vanadic salts and ammonium hydroxide or other ammonium salts react, and generates metavanadic acid Ammonia-sinking is formed sediment, and the vanadic anhydride product of higher degree is obtained after thermal decomposition.
However had in roasting process for extracting vanadium outside the inverse roaster out of the gases such as ammonia, it can be generated when with sour (sulfuric acid) leaching A large amount of waste water contain sulfate radical and sulfur dioxide in the waste water, even if being neutralized, in waste water still containing sulfate and Other harmful substances matter (such as ammonia nitrogen, remaining sulfate radical).Traditional process for extracting vanadium program is complicated, and be most difficult to control and handle It is exactly ammonia emission and wastewater treatment.If the ammonia and waste water for generating in the above process are not subject to technical treatment, not only Waste of resource, and will cause the environmental pollution to rivers lake, or even harm is generated to the drinking water source of the mankind.
Summary of the invention
The purpose of the present invention is being directed to prior art processes, can directly be extracted since smelting of digging up mine inclined Ammonium vanadate (NH4VO3) and ammonium poly-vanadate (NH4)2V6O16；With ammonium metavanadate (NH4VO3) or ammonium poly-vanadate (NH4)2V6O16It is made High purity vanadic anhydride (V2O5) during, it can the ammonia (NH that all discharges of boundling3) ammonium (NH is made4 +) use, it is ensured that exhaust gas zero Discharge；Due to using a kind of polyacid ester (R) (patent of invention product, also known as flocculant) technology, make to generate in the above process complete Portion's waste water is effectively addressed, it is ensured that whole wastewater zero discharges are recycled, and all product purities produced reach 99.5- 99.99%.
The invention is realized by the following technical scheme:
The technique that the Ammonia recovery ammonium and waste water of a kind of vanadium processed are recycled, vanadium technique processed includes: 1) to prepare metavanadic acid Ammonium and ammonium poly-vanadate；2) high purity vanadic anhydride is made in ammonium metavanadate and ammonium poly-vanadate, process includes the following steps: a, alkali It is molten.With ammonium metavanadate (NH4VO3) or ammonium poly-vanadate (NH4)2V6O16It is dissolved in alkali (NaOH), dissolves by heating ammonium metavanadate (NH4VO3) or ammonium poly-vanadate (NH4)2V6O16, a large amount of ammonia (NH can be generated at this time3), to ammonia (NH3) with water use thermal release Technology makes ammonia (NH3) entering recovery tower, vapor is fallen into reactor；B, pH value is adjusted.While dissolution, while tune acid process In, ammonia (NH3) into recovery tower, and a part of ammonia (NH3) due to acid effect generate metal ammonium (NH4 +)；C, it synthesizes. Sodium vanadate (Na3VO4) dope is in inherent ammonium (NH4 +) state, ammonia (NH cannot be volatilized3)；D, it washs.Ammonium metavanadate (NH4VO3) interior there are a large amount of sodium salts, it is necessary to it is equipped with a certain amount of ammonium (NH4 +) water (R) is protected to be washed, finally again with suitable The pure water spray of amount, obtains high-purity ammonium metavanadate (NH4VO3)；E, it dries.Ammonium metavanadate is toasted in the environment of 40-60 DEG C (NH4VO3), its moisture (H is sloughed at this temperature2O)；F, calcination.By ammonium metavanadate (NH4VO3) in 450-550 DEG C of furnace into Row conversion vanadic anhydride (V2O5), high temperature makes ammonium metavanadate (NH4VO3) in ammonium (NH4 +) promote to become ammonia (NH3), institute There is ammonia (NH3) fully enter ammonia (NH3) recovery tower or ammonia (NH3) be enriched in recyclable device.In ammonia (NH3) return Receive tower or ammonia (NH3) put into strong acid in recyclable device, boundling ammonia (NH3) various ammonium (NH are made4 +) use.
Preferably, the step of preparing ammonium metavanadate and ammonium poly-vanadate includes: ore dressing, ball mill grinding, transforming agent, balling-up is added The spherical of Φ 8-12mm is made, the vanadium material that roasts in the environment of 800 DEG C -850 DEG C balling-up, leaching, adjusts pH value, be enriched with To sodium vanadate dope or vanadic sulfate dope, turn shape, removal of impurities, synthesis ammonium metavanadate or ammonium poly-vanadate.
Preferably, leaching step are as follows: roasting vanadium (V) ball is leached, with water, acid it is any, take cold soaking Out, heating leach, any mode of shower-bubble type, having converted or well-oxygenated vanadium (V) leaches and, generation sodium vanadate (Na3VO4) solution or vanadic sulfate (VOSO4) dope.
Preferably, the step of enrichment: it is the low vanadium of 2-10g/L (V) mine product in such a way that water logging goes out to concentration, is adjusted with acid The vanadium (V) of memory can be become cation by pH value 6-5, be enriched with using the cationic resins such as 731,717, when resin is saturated Afterwards, it is stripped with sodium hydroxide (NaOH), the content of vanadium after enrichment can achieve 120-150g/L.
Preferably, with the vanadium dope of Ore Leaching, with triphenyl phosphate TPP, (C6H5O)3PO, di-(2-ethylhexyl)phosphoric acid Ester (C16H35O4P) and any of composition organic phase of extractant P-204, sulfonated kerosene are enriched with, and recycle strong acid (sulphur Acid) back extraction, vanadium dope content is enriched to 120-150g/L.
Preferably, turn shape step are as follows: go out based on water logging, alkali back extraction cool tone pH value, sodium vanadate (Na3VO4) dope encountering It will form red when sour, take the mode of heating that its acid is made mutually to break off relations with vanadium ion, dope turns shape to water shape, oily shape state.
Preferably, removal step are as follows: to guarantee ammonium metavanadate (NH4VO3) quality, turned the sodium vanadate of shape (Na3VO4) dope cleans with a kind of 2% polyacid ester (R) (patent of invention product, also known as flocculant), non-in dope Metal impurities are precipitated, precipitate, filters pressing or filtering, dope are spare.
Preferably, synthesis step are as follows: the dope got ready, be separately added into ammonium chloride (NH by the different content of vanadium4CL) 1.1 times, ammonium sulfate (NH4)2SO41.5 times or ammonium nitrate (NH4NO3) 1.8 times be stirred synthesis, what is obtained is ammonium metavanadate (NH4VO3)。
Preferably, ammonium metavanadate (NH is synthesized4VO3) way it is as follows: 1. with having synthesized ammonium metavanadate (NH4VO3) ammonium (NH4 +) mother liquid coming, it is tested through Baume hydrometer (° B á), determines that specific gravity is 24-25, by ammonium (NH4 +) mother liquid coming through thermal energy method or It is 28-29 that condensation method, which reaches specific gravity, in ammonium (NH4 +) in mother liquid coming plus 10% ammonium chloride (NH4CL), ammonium sulfate (NH4)2SO4Or Ammonium nitrate (NH4NO3) stirring and dissolving, activate ammonium (NH4 +) mother liquid coming, it is at this moment 31- with Baume hydrometer (° B á) test specific gravity 34, then again in ammonium (NH4 +) a kind of 2% polyacid ester (R) (patent of invention product, also known as flocculant) is added in mother liquor is stirred It is miscellaneous to mix analysis, removes undissolved ammonium salt, sodium and sodium salt, it is spare into synthesis phase again；2. in synthesis ammonium metavanadate (NH4VO3) When, by sodium vanadate (Na3VO4) dope content of vanadium 100-120g/L to the utmost, 1. number spare ammonium (NH4 +) mother liquid coming is by volume It is put into 45-55%, is stirred 1-2 hours, at this moment inherence has formed the ammonium metavanadate (NH of solid4VO3), upper layer dope content of vanadium is 0.2-0.5g/L, draining or drying can be obtained ammonium metavanadate (NH4VO3), the ammonium mother liquid coming used is synthesized according still further to method 1. It is carried out with operation sequence recycled.
For the vanadic sulfate dope being stripped in leaching step with Ore Leaching, strong acid, it is heated to 60-90 DEG C, is made It is neutralized to pH value 4-5 with liquid ammonium, obtains ammonium poly-vanadate (NH4)2V6O16。
The present invention has the advantages that
1, vanadium (V) ore resources are in smelting process, and roasting powder or ball acid or water logging go out, Leaching Vanadium (V) Concentration is generally 4-10g/L, it is necessary to carry out organic phase or resin enrichment processing, and be enriched with and a large amount of water is needed to handle, generally 1 ton of product of every production will generate 150-300 tons of acid waste water.
2, this technique carries out being neutralized to pH value 7.6-7.8 using lime (CaO) or sodium hydroxide (NaOH), but due to waste water It is interior containing heavy metals such as a large amount of chromium (Cr), titaniums (Ti), there are also impurity such as silicon (Si), calcium (Ca), magnesium (Mg) and soil and toxic Ingredient, different mineral resources generate different impurity, and waste water at this time can not discharge.The method of evaporating generallyd use at present also can not Regulation effect, 1 ton of vanadic anhydride (V of every production can be reached2O5) waste water that need to evaporate 150-300 tons is also unpractical；Using Relatively advanced isolation film technical treatment is also unable to reach desired effect, because the accessible conductivity of isolation film is only 300- 500S/m, and the conductivity of waste water has reached 5,000-10,000S/m at this time, not may pass through isolation film.For this purpose, this work Skill, which is taken, is added polyacid ester (R) (a kind of patent of invention product, also known as flocculant) in the waste water of sum in, and 20-30 points of stirring Clock can all be precipitated all impurity, heavy metal and toxic component, precipitating.Precipitation composition granule is tiny at this time, and suspension is not easy Precipitating.
3, this technique is using a certain proportion of unformed White Carbon black (SiO of addition2), its main function in the treatment of waste water It is: 1. adsorbs；2. removing color；3. carrying suspended impurity precipitating；4. purification etc..Therefore above-mentioned suspended matter can be made to accelerate to precipitate and be convenient for Clarification filtration.
4, this technique can directly extract ammonium metavanadate (NH since smelting of digging up mine4VO3) and ammonium poly-vanadate (NH4)2V6O16； With ammonium metavanadate (NH4VO3) or ammonium poly-vanadate (NH4)2V6O16High purity vanadic anhydride (V is made2O5) during, it can boundling row Ammonia (the NH put3) ammonium (NH is made4 +) use, it is ensured that zero waste gas emission；Due to using a kind of polyacid ester (R) (patent of invention production Product, also known as flocculant) technology, so that whole waste water of above process generation is effectively addressed, it is ensured that wastewater zero discharge, circulation make With, and the purity for producing all products reaches 99.5-99.99%.
5, " filter solid conversion attractant is crossed containing vanadium in navajoite smelting roasting process " caused by this technique, applicant country Family's patent (patent No.: 201711297727.0), can make conversion of the independent product for navajoite product.
6, " the polyacid ester " used in the present invention be the phosphate diester being concentrated, and is a kind of patent of invention product, also known as flocculant, In Jiangsu granary, long weathering factory is on sale.
Specific embodiment
Below by exemplary embodiment, the present invention will be further elaborated, but these examples are not intended to limit this hair The material of bright range, all technologies realized based on above content of the present invention is all belonged to the scope of protection of the present invention.
One, since digging up mine and smelting, " one-step method " can be made into ammonium metavanadate (NH4VO3) and ammonium poly-vanadate (NH4)2V6O16
Thick navajoite is leached and obtains sodium vanadate dope (according to different process, different thick content of vanadium is prepared difference and contained Amount) ammonium metavanadate (NH is made4VO3) and ammonium poly-vanadate (NH4)2V6O16.Its process flow is general are as follows:
1, navajoite.Vanadium slag containing vanadium (V), vanadium mud or the gangue containing vanadium.
2, ore dressing.Other sundries of non-vanadium (V) are removed in choosing.
3, it crushes.Ball mill grinding is carried out to slag, mud, stone containing vanadium (V).
4, add transforming agent.Different transforming agent or oxidant are added to different vanadium (V) mineral resources, such as soda ash (Na2CO3), again Spar (BaSO4) or other barium salts, salt (NaCL) can also be added.
5, balling-up.The spherical of Φ 8-12mm is made in low-grade vanadium (V) ore resources, such as vanadium oxidation mud, gangue, it is high Vanadium (V) ore resources of grade can also use powder.
6, it roasts.The vanadium material of powder and balling-up to milled roasted in the environment of 800 DEG C -850 DEG C (or burn Burn), so that vanadium (V) is achieved the purpose that conversion and oxidation with different roasters or different equipment.
7, it leaches.Roasting vanadium (V) powder or vanadium (V) ball are leached, with water acid, cold soaking can be taken to go out, Heating can also be taken to leach, it more can shower-bubble type, it is therefore an objective to having converted or well-oxygenated vanadium (V) leaches and, generation sodium vanadate (Na3VO4) dope or vanadic sulfate (VOSO4) dope.
8, pH value is adjusted.PH value is adjusted according to different extraction modes, such as there is no need to adjust pH value using Ore Leaching mode.
9, it is enriched with.It is to low vanadium (V) mine product in such a way that water logging goes out, general concentration is in 2-10g/L, it is therefore necessary to acid PH value 6-5 is adjusted, the vanadium (V) of memory can be become cation, is enriched with using the cationic resins such as 731,717, works as resin It after saturation, is stripped with sodium hydroxide (NaOH), the content of vanadium after enrichment generally can reach 120-150g/L.Such as use Ore Leaching , phosphoric acid triphenylmethyl methacrylate [TPP, (C6H5O)3PO] it leaches, or with di-(2-ethylhexyl)phosphoric acid ester (C16H35O4P it) and extracts Agent P-204, or be enriched with the composition organic phase of sulfonated kerosene, recycle strong acid (sulfuric acid) back extraction, this extracting process Equally vanadium dope content can be enriched to 120-150g/L.
10, it obtains.Thus sodium vanadate (Na is obtained3VO4) dope or vanadic sulfate (VOSO4) dope.Gone out with water logging, acid extraction It takes, alkali is stripped is sodium vanadate (Na3VO4) dope, and the dope of Ore Leaching, strong acid back extraction should be known as vanadic sulfate (VOSO4) dope.
11, pH value is adjusted.Since the method for enrichment and the technique of back extraction are different, and resulting vanadium dope is also just different, water What is leached is stripped using sodium hydroxide (NaOH), and what is obtained is alkaline dope, also referred to as sodium vanadate (Na3VO4) dope, so PH value 7.8-8.5 must be adjusted spare, and the dope of Ore Leaching, strong acid back extraction is just not required to adjusting pH value spare again.
12, turn shape.Gone out based on water logging, alkali back extraction cool tone pH value, makes sodium vanadate (Na3VO4) dope meeting shape when encountering acid At red, it is necessary to take the mode suitably heated that its acid is made mutually to break off relations with vanadium ion, dope turns shape to water shape, oily shape state (acid Property leach, strong acid back extraction be detailed in 4).
13, it cleans.To guarantee ammonium metavanadate (NH4VO3) quality, turned the sodium vanadate (Na of shape3VO4) dope is necessary It is cleaned with a kind of 2% polyacid ester (R) (patent of invention product, also known as flocculant), the nonmetallic inclusion in dope is analysed Out, precipitating, filters pressing or filtering, dope are spare (Ore Leaching, strong acid back extraction are detailed in 4).
14, it synthesizes.The above-mentioned dope got ready, chlorination is separately added by the different content (1+1.2-1.6 etc.) of vanadium Ammonium (NH4CL), ammonium sulfate [(NH4)2SO4] or ammonium nitrate (NH4NO3) it is stirred synthesis, what is obtained is ammonium metavanadate (NH4VO3)。
Synthesize ammonium metavanadate (NH4VO3) way it is as follows:
1. with ammonium metavanadate (NH has been synthesized4VO3) ammonium (NH4 +) mother liquid coming, it tests, determines through Baume hydrometer (° B á) Specific gravity is 24-25, by ammonium (NH4 +) mother liquid coming through thermal energy method or condensation method measure specific gravity be 28-29, in ammonium (NH4 +) mother liquid coming In plus 10% ammonium chloride (NH4CL), ammonium sulfate (NH4)2SO4Or ammonium nitrate (NH4NO3) stirring and dissolving, activate ammonium (NH4 +) female At this moment liquid water is 31-34 with Baume hydrometer (° B á) test specific gravity, then again in ammonium (NH4 +) 2% polyacid is added in mother liquor Ester (R) (a kind of patent of invention product, also known as flocculant) be stirred analysis it is miscellaneous, remove undissolved ammonium salt, sodium and sodium salt, enter Synthesis phase is spare again.
2. in synthesis ammonium metavanadate (NH4VO3) when, by sodium vanadate (Na3VO4) dope content of vanadium 100-120g/L to the utmost, 1. number spare ammonium (NH4 +) mother liquid coming is put into 45-55% by volume, it stirs 1-2 hour, at this moment inherence has formed the inclined of solid Ammonium vanadate (NH4VO3), upper layer dope content of vanadium is 0.2-0.5g/L, and draining or drying can be obtained ammonium metavanadate (NH4VO3)。 Synthesize the ammonium mother liquid coming that uses according still further to 1. method and operation sequence carry out it is recycled.
If 60-90 DEG C should be heated to what Ore Leaching, strong acid were stripped, it is neutralized to pH value 4-5 using liquid ammonium, can be obtained To ammonium poly-vanadate [(NH4)2V6O16】。
Two, with ammonium metavanadate (NH4VO3) or ammonium poly-vanadate [(NH4)2V6O16] high purity vanadic anhydride (V is made2O5) process In, it realizes whole Ammonia recoveries and ammonium use is made.
Process flow and the production method is as follows:
1, alkali soluble.With ammonium metavanadate (NH4VO3) or ammonium poly-vanadate [(NH4)2V6O16] high purity vanadic anhydride (V is made2O5) Method Shi Bixu molten using alkali (NaOH), due to being to dissolve by heating ammonium metavanadate (NH during alkali (NaOH) is molten4VO3) Or ammonium poly-vanadate [(NH4)2V6O16], a large amount of ammonia (NH will necessarily be generated3), it at this moment must use ammonia (NH3) hot with water progress Isolation technics, ammonia (NH3) entering recovery tower, vapor is then naturally fallen in reactor.
2, pH value is adjusted.While dissolution, while tune it is sour during, ammonia (NH3) into recovery tower, and some is due to acid Under the action of generate metal ammonium (NH4 +), also with regard to benefit benefit ammonia (NH3) regeneration and purification.
3, it synthesizes.Due to sodium vanadate (Na3VO4) ammonium (NH of the dope in inherence4 +) state, it is also impossible to volatilize ammonia Gas (NH3)。
4, it washs.High-purity ammonium metavanadate (NH4VO3) obtain, be in ammonium vanadate (NH4VO3) obtain in alkali (NaOH) dope , this just makes ammonium metavanadate (NH4VO3) interior there are a large amount of sodium salts, it is necessary to it is equipped with a certain amount of ammonium (NH4 +) protection water (R) into Row washing (otherwise sodium vanadate can be dissolved in water), finally obtains high-purity ammonium metavanadate with suitable pure water spray again (NH4VO3)。
5, it dries.Ammonium metavanadate (NH is toasted in the environment of 40-60 DEG C4VO3), due to its internal factor, at this temperature Its moisture (H can only be sloughed2O) can not volatilize ammonia (NH3)。
6, calcination.By ammonium metavanadate (NH4VO3) conversion vanadic anhydride (V is carried out in 450-550 DEG C of furnace2O5), it is high Temperature makes ammonium metavanadate (NH4VO3) in ammonium (NH4 +) promote to become ammonia (NH3), it at this moment must be all ammonia (NH3) all defeated Enter ammonia (NH3) recovery tower or ammonia (NH3) be enriched in recyclable device.In ammonia (NH3) recovery tower or ammonia (NH3) return In receiving apparatus, such as puts into hydrochloric acid (HCL) and generate ammonium chloride (NH4Cl)；Put into sulfuric acid (H2SO4) generate ammonium sulfate (NH4)2SO4；It throws Enter nitric acid (NHO3) generate ammonium nitrate (NH4NO3).This technique the result is that achieve many things at one stroke, both obtained high purity vanadic anhydride (V2O5), and the whole ammonia (NH of boundling3) ammonium (NH has been made4 +) use.Both ammonia (NH had been prevented3) volatilization, purified sky Gas, and reduce costs, increase economic benefit.
The above is only illustrating for possible embodiments of the invention, but the embodiment is not intended to limit the invention The scope of the patents, all equivalence enforcements or change without departing from carried out by thinking of the present invention are intended to be limited solely by the scope of the patents of the invention In.

Claims (10)

1. the technique that the Ammonia recovery ammonium and waste water of a kind of vanadium processed are recycled, vanadium technique processed includes: 1) to prepare ammonium metavanadate And ammonium poly-vanadate；2) high purity vanadic anhydride is made in ammonium metavanadate and ammonium poly-vanadate, feature and process include the following steps: A, alkali soluble: ammonium metavanadate (NH is used4VO3) or ammonium poly-vanadate (NH4) 2V6O16It is dissolved in alkali (NaOH), dissolves by heating ammonium metavanadate (NH4VO3) or ammonium poly-vanadate (NH4) 2V6O16A large amount of ammonia (NH can be generated3), using ammonia (NH3) and water progress thermal release skill Art, ammonia (NH3) entering recovery tower, vapor is fallen into reactor；B, adjust pH value: while dissolution, while tune it is sour during, ammonia Gas (NH3) into recovery tower, and some ammonia (NH3) due to generating metal ammonium (NH under the action of acid4 +)；C, it synthesizes: Sodium vanadate (Na3VO4) ammonium (NH of the dope in inherence4 +) state, ammonia (NH cannot be volatilized3)；D, it washs: ammonium metavanadate (NH4VO3) interior there are a large amount of sodium salts, it is necessary to it is equipped with a certain amount of ammonium (NH4 +) flocculant polyacid ester washed, finally used again Suitable pure water spray obtains high-purity ammonium metavanadate (NH4VO3)；E, it dries: toasting ammonium metavanadate in the environment of 40-60 DEG C (NH4VO3), its moisture (H is sloughed at this temperature2O)；F, calcination: by ammonium metavanadate (NH4VO3) in 450-550 DEG C of furnace into Row conversion vanadic anhydride (V2O5), high temperature makes ammonium metavanadate (NH4VO3) in ammonium (NH4 +) promote to become ammonia (NH3), institute There is ammonia (NH3) fully enter ammonia (NH3) recovery tower or ammonia (NH3) be enriched in recyclable device, in ammonia (NH3) return Receive tower or ammonia (NH3) ammonium is made in investment strong acid in recyclable device.
2. the technique that the Ammonia recovery ammonium and waste water of vanadium processed according to claim 1 are recycled, which is characterized in that system The step of standby ammonium metavanadate and ammonium poly-vanadate includes: ore dressing, ball mill grinding, transforming agent is added, the ball of Φ 8-12mm is made in balling-up Shape, the material containing navajoite that balling-up is roasted in the environment of 800 DEG C -850 DEG C, leaching, adjusting pH value, enrichment obtain sodium vanadate dope Or vanadic sulfate dope, turn shape, removal of impurities, synthesis ammonium metavanadate or ammonium poly-vanadate.
3. the technique that the Ammonia recovery ammonium and waste water of vanadium processed according to claim 2 are recycled, which is characterized in that leaching Step out are as follows: roasting vanadium (V) ball is leached, with water, acid it is any, take cold soaking go out, heating leach, spray leaching Any mode out, converted or well-oxygenated vanadium (V) leach come, generate sodium vanadate (Na3VO4) dope or vanadic sulfate (VOSO4) dope.
4. the technique that the Ammonia recovery ammonium and waste water of vanadium processed according to claim 2 are recycled, which is characterized in that rich The step of integrating: it is the low vanadium of 2-10g/L (V) mine product in such a way that water logging goes out to concentration, PH value 6-5 is adjusted with acid, memory Vanadium (V) can become cation, be enriched with using the cationic resins such as 731,717, after resin saturation, use sodium hydroxide (NaOH) it is stripped, the vanadium dope content after enrichment can achieve 120-150g/L.
5. the technique that the Ammonia recovery ammonium and waste water of vanadium processed according to claim 2 are recycled, which is characterized in that use The vanadium dope of Ore Leaching, with triphenyl phosphate TPP, (C6H5O)3PO leach, or with di-(2-ethylhexyl)phosphoric acid ester ( C16H35O4P it extractant P-204 or is enriched with) and with any of composition organic phase of sulfonated kerosene, recycles strong acid (sulphur Acid) back extraction, vanadium dope content is enriched to 120-150g/L.
6. the technique that the Ammonia recovery ammonium and waste water of vanadium processed according to claim 2 are recycled, which is characterized in that turn Shape step are as follows: gone out based on water logging, alkali back extraction cool tone pH value, make sodium vanadate (Na3VO4) dope will form red when encountering acid, Take the mode of heating that its acid is made mutually to break off relations with vanadium ion, dope turns shape to water shape, oily shape state.
7. the technique that the Ammonia recovery ammonium and waste water of vanadium processed according to claim 2 are recycled, which is characterized in that remove Miscellaneous step are as follows: to guarantee ammonium metavanadate (NH4VO3) quality, turned the sodium vanadate (Na of shape3VO4) dope with 2% polyacid ester (R) clean, in dope nonmetallic inclusion be precipitated, precipitating, filters pressing or filtering, dope it is spare.
8. the technique that the Ammonia recovery ammonium and waste water of vanadium processed according to claim 1 are recycled, which is characterized in that close At step are as follows: the dope got ready, be separately added into ammonium chloride (NH by the different content of vanadium4CL), ammonium sulfate (NH4) 2SO4Or Ammonium nitrate (NH4NO3) it is stirred synthesis, that obtain is ammonium metavanadate (NH4VO3).
9. the technique that the Ammonia recovery ammonium and waste water of vanadium processed according to claim 1 are recycled, which is characterized in that close At ammonium metavanadate (NH4VO3) way it is as follows: 1. with having synthesized ammonium metavanadate (NH4VO3) ammonium (NH4 +) mother liquid coming, through Baume Densimeter test determines that specific gravity is 24-25, by ammonium (NH4 +) mother liquid coming through thermal energy method or condensation method measure specific gravity be 28-29, In ammonium (NH4 +) in mother liquid coming plus 10% ammonium chloride (NH4CL), ammonium sulfate (NH4) 2SO4Or ammonium nitrate (NH4NO3) stirring and dissolving, Activate ammonium (NH4 +) mother liquid coming, it is at this moment 31-34 with Baume hydrometer (° B á) test specific gravity, then again in ammonium (NH4 +) in mother liquor Be added 2% polyacid ester (R) (a kind of patent of invention product, also known as flocculant) be stirred analysis it is miscellaneous, remove undissolved ammonium salt, Sodium and sodium salt, it is spare into synthesis phase again；2. in synthesis ammonium metavanadate (NH4VO3) when, by sodium vanadate (Na3VO4) dope vanadium Content 100-120g/L to the utmost, 1. number spare ammonium (NH4 +) mother liquid coming is put into 45-55% by volume, it stirs 1-2 hours, this When it is interior in the ammonium metavanadate (NH for having formed solid4VO3), upper layer dope content of vanadium is 0.2-0.5g/L, and draining or drying can obtain To ammonium metavanadate (NH4VO3), the ammonium mother liquid coming that uses of synthesis according still further to 1. method and operation sequence carry out it is recycled.
10. the technique that the Ammonia recovery ammonium and waste water of vanadium processed according to claim 1 are recycled, which is characterized in that The vanadic sulfate dope being stripped in leaching step with Ore Leaching, strong acid, is heated to 60-90 DEG C, is neutralized to using liquid ammonium PH value 4-5 obtains ammonium poly-vanadate (NH4) 2V6O16。
CN201811068047.6A 2018-09-13 2018-09-13 The technique that the Ammonia recovery ammonium and waste water of a kind of vanadium processed are recycled Pending CN109081375A (en)

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CN201811068047.6A CN109081375A (en) 2018-09-13 2018-09-13 The technique that the Ammonia recovery ammonium and waste water of a kind of vanadium processed are recycled
US16/565,828 US10974968B2 (en) 2018-09-13 2019-09-10 Process for recovering ammonia from vanadium preparation for ammonium preparation and recycling wastewater
RU2019128406A RU2710613C1 (en) 2018-09-13 2019-09-10 Method of reducing ammonia from a vanadium compound for producing an ammonia compound and recycling waste water
DE102019124431.5A DE102019124431A1 (en) 2018-09-13 2019-09-11 Process for the recovery of ammonia from the vanadium treatment for ammonium treatment and for wastewater reuse
PCT/CN2019/105945 WO2020052686A1 (en) 2018-09-13 2019-09-16 Process for preparing ammonium from vanadium-producing ammonia gas and recycling wastewater

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